Detergent composition

ABSTRACT

A CONTROLLED FOAM PROFILE DETERGENT COMPOSITION CONTAINING A C11 TO C13 ALKYL BENZENE SULFONATE, A SODIUM SOAP OF C14 TO C22 FATTY ACID AND AN ETHOXYLATED DINONYL PHENOL. THE COMPOSITION CAN ALSO CONTAIN AN ALKALINE BUILDER SALT.

3,826,749 Patented July 30, 1974 DETERGENT COMPOSITION M. Yvon Demangeon, Ermont, France, and M. Per Hjorth Rasmussen, Copenhagen, Denmark, assignors to C01- gate-Palmolive Company, New York, N.Y.

No Drawing. Filed Jan. 24, 1972, Ser. No. 220,480 Int. Q]. C11d 9/32 US; Cl. 252121 3 Claims ABSTRACT OF THE DISCLOSURE A controlled foam profile detergent composition containing a C to C alkyl benzene sulfonate, a sodium soap of C to C fatty acid and an ethoxylated dinonyl phenol. The composition can also contain an alkaline builder salt.

It is well known that detergents intended for use in drum-type washing machines have to be low-foaming in order to avoid foam over-spilling during the washing process. Numerous no foaming products are presently available commercially, but these products are scarcely used to perform other types of laundry washingparticularly hand washingbecause the absence of foam in the pan makes their use unpleasant and gives a feeling of inefficacy.

' One aspect of this invention relates to a novel detergent composition which while giving a desirable low foam in the washing machine, produces and ample and stable foam rapidly in the pan. The composition is especially useful in hard water such as water whose hardness is well over 150 p.p.m.

A preferred composition according to this invention comprises a blend of three detergents: a sodium higher alkylbenzenesulfonate having about 11 to 13 carbon atoms in its alkyl group, a sodium soap of a fatty acid of C to C carbon atoms and ethoxylated dinonylphenol containing an average of 12 to 30 mols of ethylene oxide per mol of the phenol, and preferably also having a cloud point of greater than about 50 C. up to 85 C. as a 1% solution in water.

The proportions are preferably such that the alkylbenzenesulfonatezsoap ratio is in the range of about 6:1 to 1:6, the alkylbenzenesulfonate:ethoxylated dinonyl phenol ratio is in the range of about :1 to 1:5 and the ratio of fatty acid soap to ethoxylated dinonyl phenol is from about 4:1 to 1:4.

Preferably there is used a linear alkylbenzenesulfonate having a high content of 3- (or higher) phenyl isomers and a correspondingly low content (well below 50%) of 2- (or lower) phenyl isomers; in other terminology, the benzene ring is preferably attached in large part at the 3- or higher (e.g. 4, 5, 6, or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2- or 1- position is correspondingly low. Particularly preferred materials are set forth in US. Pat. 3,320,174, patented May 16, 1967, of J Rubinfeld. It is within the broader scope of the invention to use branched chain alkylbenzenesulfonates, as such or in admixture with linear alkylbenzenesulfonates.

Especially good results are obtained, particularly when the linear alkylbenzenesulfonates are used, when the ethoxylated dinonyl phenol conforms to the following specifications:

1. Cloud point (as a 1% solution in water)about 50 C. to 80 C., preferably 55 C. to 65 0., most preferably about 57 C. to 63 0.;

2. Average number of mols of ethylene oxide per mol of phenolabout 15 to 17, most preferably about 15.5 to 16.5;

3. Hydroxyl value-about 51 to 56, most preferably about 52 to 55;

4. Monomonyl' phenol content of the dinonyl phenol from which the ethoxylated product is producedless than about 25%, more preferably less than about and most preferably less than about 15%;

5. Polyethylene .glycol contentless than about 5%,

and most preferably less than about 3 6. Water contentgenerally less than about 1%.

The preferred compositions are built heavy duty laundry detergents containing from 0 to 35% alkaline builder salts. A particularly useful builder salt is pentasodium tripolyphosphate (TPP) and the builder salt is preferably present in amount well in excess of the total amount of detergent, e.g. the ratio of the amount of builder salt to the total amount of detergents (organic) may be in the range of about 1:1 to 10: 1. In typical compositions the total concentration of detergents is in the range of about 5% to 35% of the total composition. Alkaline builder salts include the phosphates and particularly the condensed phosphates (e.g. pyrophosphates and tripolyphosphates, etc.), silicates, borates, and carbonates (including bicarbonates), as well as organic builders such as salts of nitrilotriacetic acid or ethylenediaminetetraacetic acid. Sodium and potassium salts are preferred. Specific examples are sodium tripolyphosphate (previously mentioned), potassium pyrophosphate, sodium hexametaphosphate, sodium carbonate, sodium bicarbonate, sodium sesquicarbonate, sodium tetraborate, sodium silicate, salts (e.g. sodium, potassium, ammonium, etc.) of methylene diphosphonic acid, disodium diglycollate, trisodium nitrilotriacetate, or mixtures of such builders, including mixtures of pentasodium tripolyphosphate and trisodium nitrioltriacetate in a ratio, of these two builders, of 1:10 to 10:1, e.g. 1:1.

The mixtures may also contain optical brightening agents or fluorescent dyes (e.g. in amounts in the range of about V to /2%); up to 5% of germicidal ingredients such as halogenated carbanilides, e.g. trichlorocarbanilide, halogenated salicylanilides, e.g. tribromosalicylanilide, halogenated bisphenols, e.g. hexachlorophene, halogenated trifiuoromethyl-diphenyl urea, zinc salt of l-hydroxy- 2-pyridinethione and the like (e.g. in amounts in the range of about to 2% soil-suspending agents such as sodium carboxymethyl cellulose or polyvinyl alcohol, preferably both, or other soluble polymeric materials, such as methyl cellulose (the amount of suspending agent being, for example, in the range of about to 2%); antioxidants such as 2,6-di-tert-butyl phenol, or other phenolic antioxidant materials (e.g. in amounts in the range of about 0.001% to 0.1% coloring or perfuming agents; from 0 to 40% of bleaching agents (such as perborates, e.g. sodium perborate tetrahydrate or sodium perborate monohydrate, percarbonates or chloroisocyanurates) and from 0 to 5% of enzymes such as proteolytic enzymes which are active upon protein matter and catalyze digestion or degradation of such matter when present as in a fabric stain in a hydrolysis reaction. Especially suitable enzymes are the sutilisin enzymes manufactured and cultivated from special strains or spore forming bacteria, particularly Bacillus subtilis. An amylase (e.g. bacterial amylase of the alpha type) may be present instead of, or in addition to, the proteolytic enzyme The composition may further contain from 0 to 10% of a fatty amine, e.g., a C to C fatty amine. The fatty amine may be a C to C secondary fatty amine, e.g., from 0.5 to 6%.

As a general guide for producing formulations under this invention, the following weight ranges of ingredients are operable within the ratios specified above:

Example 1 The composition used in this Example is a mixture containing three detergents, namely, 8% of sodium higher alkylbenzenesulfonate, 3% of sodium tallow soap, and 2.5% of dinonyl phenol-ethylene oxide adduct (in which the mo] ratio of ethylene oxide to the phenol is 16:1), together with 37% pentasodium tripolyphosphate (TPP), 7.1% sodium silicate (whose Na O:SiO mol ratio is 1:2.0), 1% borax, 27% sodium perborate tetrahydrate, 0.7% sodium carboxymethylcellulose, 0.2% sodium edetate (tetra sodium salt of ethylenediaminetetraacetic acid), 0.7% of proteolytic enzyme preparation (Alcalase, which is a proteolytic sutilisin enzyme preparation available from Novo Industria A/ S, Copenhagen, Denmark) whose activity, measured at pH 7.5 is about 1.5 Anson Units per gram, and about 0.3% of optical brighteners. The composition contains water; its total moisture content (including water of hydration which is present, for exafple, in the borax, sodium perborate tetrahydrate, and TPP) about 18.4%. It also contains a balance of sodium sulfate and a very small amount of coloring matter (such as Iragon Blue LUD).

The composition is prepared by mixing a long chain linear alkylbenzenesulfonic acid, whose alkyl chains have mainly 10 to 14 carbon atoms, the average length of the alkyl chains being 12 carbon atoms, the alkyl chain distribution being:

Percent C and under 20 maximum C 20 minimum C 25 minimum C 20 minimum C and over 10 maximum with distilled tallow fatty acids and the dinonyl phenolethylene oxide adduct, adding aqueous caustic soda to neutralize the acids, and then blending the resulting aqueous mixture with the other ingredients (except for the sodium perborate and enzyme preparation) to form a slurry which is spray dried, so as to form a granular product in which the granules are hollow beads or clusters of such beads. To this granular product there are added granular sodium perborate tetrahydrate and the enzyme preparation (also in granular form, as a blend containing 25% Alcalase, 25% tetrapotassium pyrophosphate, 1.4% nonionic detergent (C linear alcohol plus mols of ethylene oxide) and the balance sodium tripolyphosphate (TPP).

The dinonyl phenol-ethylene oxide adduct has the following characteristics:

Cloud Point (1% in water) C-.. 62 Density g./ml 1.04 Pour Point C..- 22 HLB Value -13.4 Surface Tension (2 0 C.--dynes/cm.

The dinonyl moiety is derived from trimerizing propylene to give a tripropylene substituent (two of such substituents in the instant product).

The composition is tested for its foaming properties in the basin and in a front loading washing machine, using water of 250 p.p.m. hardness. (The calcium to magnesium ra o bei g The tests in the basin are made at 0.5 and 1%, concentrations, i.e. or 100 grams of the composition are poured into a basin containing 10 liters of water and the foam is generated by hand. In each case a copious stable foam is produced rapidly, the results being similar to those obtained when a commercial built detergent product is tested in the same way, except that the foam from the latter is less stable.

The tests in the washing machine are made with a Miele 421 washing machine, using the composition at 0.5% concentration, using clean cotton towels as the load in the machine (3 kilograms of the towels in about 18 kilograms of wash water), with the machine set to the cycle for heavy soiled clothes. The foam height is measured during the foaming cycle. An excellent foam profile is obtained with the composition of this invention, whereas the commercial product overfoams.

The comparative tests are repeated using water having a hardness of 400 ppm. Here again the product of this Example gives a copious stable foam rapidly. The results at the 0.5% concentration are similar to those obtained when another commercial built detergent product is tested in the same way; in the test a 1% concentration the foam from that commercial product is far less stable than that from the product of this Example. In tests in the Miele 421 washing machine at 0.4% concentration (again using the clean towels as the load and the cycle for heavily soiled clothes) the foam profile of the composition of this invention is excellent whereas the commercial product overfoams.

The Miele 421 washing machine is equipped with a device which heats the water automatically during washing, the temperatures at various times during the cycle for heavily soiled clothes being as follows:

Time (minutes): Temperature C.)

Example 2 Example 1 is repeated except that the amount of TPP is increased to 45% of the total formulation and the borax and sodium perborate are omitted, as is the sodium EDTA. The enzyme is supplied as a mixture containing 11% Alcalase, TPP and 19% water. The total moisture content of the whole composition is 12% and the balance (about 18%) is sodium sulfate. The concentration of the optical brighteners is 0.2%. The results are, again, excellent.

Example 3 Example 1 is again repeated except that the amount of TPP is reduced to 20%, the amount of sodium silicate is 3%, the amount of sodium carboxymethylcellulose is 1% and the borax, sodium perborate and sodium EDTA are omitted. The optical brighteners are present to the extent of 0.18% of the total composition. The foam profile curve which is obtained is outstanding.

Example 4 Example 1 is still once more repeated except that a branched chain sodium dodecylbenzene sulfonate is used in place of the linear sulfonate of Example 1. This composition while generally satisfactory shows more foam development midway in the washing cycle than the same composition employing the linear sulfonate.

Example 5 Example 1 is repeated once more except that the dinonyl phenol ethoxylate has the following characteristics:

Cloud Point (1% in water) C 55 Density 1.04 Pour Point C 23 Surface Tension (25 C.; 0.1% solution in water) dynes/cm. 30 Ethylene oxide content percent 65 Polyols (polyglycols, e.g., polyethylene glycols) percent 1 Example 6 Example 8 Example 1 is repeated to include, additionally 1% di- (hydrogenated tallow) amine. An excellent foam profile is obtained when tested as in Example 1.

Example 9 Example 1 is again reformulated to replace all of the phosphate with an equal weight of sodium nitrilotriacetate. Comparable results are obtained.

6 Example 10 Example 9 is repeated to include 1% di(hydrogenated tallow) amine as a further additive. Once more the results in the testing procedures are comparable.

What is claimed is:

1. A controlled foam profile detergent composition consisting essentially of A. a C to C alkyl benzene sulfonate,

B. a sodium soap of a C to C fatty acid, and

C. an ethoxylated dinonyl phenol containing an average of 12 to 30 mols of ethylene oxide per mol of the phenol wherein the ratio of A to B ranges from 6:1 to 1:6; the ratio of A to C ranges from 5:1 to 1:5, and the ratio of B to C ranges from 4:1 to 1:4.

2. A composition as defined in claim 1 including an alkaline builder salt, the ratio of builder to total detergent being from about 1:1 to 10:1.

3. A composition as defined in claim 2 wherein the range of A is 2 to 20%,

B is 1 to 12%, and

C is 1 to 10%, all on a weight basis.

References Cited UNITED STATES PATENTS 3,684,723 8/1972 Best et al 252358 X 3,215,633 11/1965 Grifo 252358 X 2,976,240 3/1961 Gilbert et al. 252358 X 2,954,347 9/1960 St. John et al 252109 3,366,570 1/1968 Slob 25297 X MAYER WEINBLATI', Primary Examiner US. Cl. X.R. 

